Determination of Urinary PAH Metabolites Using DLLME Hyphenated to Injector Port Silylation and GC–MS-MS

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants and well-known carcinogens. Hydroxy derivatives of PAH are considered as biomarkers of PAH exposure, and there is a need to measure these metabolites at low concentrations. So, a precise and eco-friendly analytical method has been developed for rapid determination of PAH metabolites. For the first time, a new analytical method based on coupling of dispersive liquid–liquid microextraction (DLLME) with auto-injector port silylation (auto-IPS) followed by gas chromatography–tandem mass spectrometry (GC–MS-MS) analysis is reported for the analysis of seven urinary PAH metabolites. Factors affecting DLLME and IPS, such as type and volume of extraction and disperser solvent, pH, ionic strength, injector port temperature, volume of N,O-bis(trimethylsilyl)trifluoroacetamide and type of solvent were investigated. Under optimized conditions, the limit of detection and limit of quantification were found to be in the range of 1–9 and 3–29 ng/mL, respectively. Satisfactory recoveries of metabolites in urine samples in the range of 87–95% were found. The developed method has been successfully applied for the determination of PAH metabolites in urine samples of exposed workers. DLLME–auto-IPS–GC–MS-MS method is time, labor, solvent and reagent saving, which can be routinely used for the analysis of urinary PAH metabolites.